Composition for organic optoelectronic element, organic optoelectronic element, and display device

ABSTRACT

The present invention relates to a composition for an organic optoelectronic element, containing: at least one first compound represented by formula 1; and at least one second compound represented by formula 2, to an organic optoelectronic element comprising the same, and to a display device comprising the organic optoelectronic element. 
     Here, formulas 1 and 2 are as described in the specification.

CROSS REFERENCE TO RELATED APPLICATIONS

This is the U.S. national phase application based on PCT Application No.PCT/KR2016/011323, filed Oct. 10, 2016, which is based on Korean PatentApplication No. 10-2015-0148231 filed Oct. 23, 2015 and Korean PatentApplication No. 10-2016-0129962 filed Oct. 7, 2016, the entire contentsof all of which are hereby incorporated by reference.

TECHNICAL FIELD

An organic optoelectronic device and a display device are disclosed.

BACKGROUND ART

An organic optoelectronic device (organic optoelectric diode) is adevice that converts electrical energy into photoenergy, and vice versa.

An organic optoelectronic device may be classified as follows inaccordance with its driving principles. One is a photoelectric devicewhere excitons are generated by photoenergy, separated into electronsand holes, and are transferred to different electrodes to generateelectrical energy, and the other is a light emitting device where avoltage or a current is supplied to an electrode to generate photoenergyfrom electrical energy.

Examples of the organic optoelectronic device are an organicphotoelectric device, an organic light emitting diode, an organic solarcell, and an organic photo conductor drum.

Of these, an organic light emitting diode (OLED) has recently drawnattention due to an increase in demand for flat panel displays. Theorganic light emitting diode is a device converting electrical energyinto light by applying current to an organic light emitting material,and has a structure in which an organic layer is disposed between ananode and a cathode.

A blue organic light emitting diode having a long life-span isconsidered to be one of the critical factors for realizing a longlife-span full color display. Accordingly, development of a blue organiclight emitting diode having a long life-span is being activelyresearched. In order to solve this problem, a blue organic lightemitting diode having a long life-span is provided in this invention.

DISCLOSURE Technical Problem

An embodiment provides an organic optoelectronic device capable ofrealizing high efficiency and long life-span characteristics.

Another embodiment provides an organic optoelectronic device includingthe composition for an organic optoelectronic device.

Yet another embodiment provides a display device including the organicoptoelectronic device.

Technical Solution

According to one embodiment, a composition for an organic optoelectronicdevice includes at least one first compound represented by formula 1 andat least one second compound represented by formula 2.

In formula 1,

X¹ to X¹² are independently N, C, or CR^(a),

at least one of X¹ to X⁶ is N,

at least one of X⁷ to X¹² is N,

R^(a)'s are independently hydrogen, deuterium, a substituted orunsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynylgroup, a substituted or unsubstituted C6 to C30 aryl group, asubstituted or unsubstituted C6 to C30 aryloxy group, a substituted orunsubstituted C6 to C30 arylthio group, a substituted or unsubstitutedC2 to C30 heteroaryl group, a hydroxyl group, a thiol group, or acombination thereof,

R^(a)'s are independently present or adjacent R^(a)'s are linked witheach other to provide a ring, and

L¹ is a C6 to C30 arylene group that is unsubstituted or substitutedwith deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, or a C6 toC30 aryl group;

In formula 2,

L² to L⁴ are independently a single bond, a substituted or unsubstitutedC6 to C30 arylene group, or a substituted or unsubstituted C2 to C30heteroarylene group,

Ar¹ to Ar³ are independently, a substituted or unsubstituted C6 to C30aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group,or a combination thereof, and

when specific definition is not otherwise provided, “substituted” offormulas 1 and 2 refers to replacement of at least one hydrogen bydeuterium, a halogen, a hydroxyl group, an amino group, a C1 to C30amine group, a C6 to C30 arylamine group, a nitro group, a C1 to C40silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkylgroup, or a cyano group.

According to another embodiment, an organic optoelectronic deviceincluding the composition for an organic optoelectronic device isprovided.

According to yet another embodiment, a display device including theorganic optoelectronic device is provided.

Advantageous Effects

An organic optoelectronic device having high efficiency and a longlife-span may be realized.

DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are schematic cross-sectional views of an organicoptoelectronic device according to an embodiment.

DESCRIPTION OF SYMBOLS

-   -   100, 200: organic light emitting diode    -   105: organic layer    -   110: cathode    -   120: anode    -   130: light emitting layer    -   140: auxiliary layer

BEST MODE

Hereinafter, embodiments of the present invention are described indetail. However, these embodiments are exemplary, the present inventionis not limited thereto and the present invention is defined by the scopeof claims.

In the present specification, when a definition is not otherwiseprovided, “substituted” refers to replacement of at least one hydrogenof a substituent or a compound by deuterium, a halogen, a hydroxy group,an amino group, a C1 to C30 amine group, a C6 to C30 arylamine group, anitro group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 toC30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, aC1 to C10 trifluoroalkyl group, or a cyano group.

In addition, two adjacent substituents of the substituted C1 to C30amine group, C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkylgroup, C6 to C30 aryl group, C2 to C30 heterocyclic group, or C1 to C20alkoxy group may be linked with each other to form a fused ring. Forexample, the substituted C6 to C30 aryl group may be linked with anotheradjacent substituted C6 to C30 aryl group to form a substituted orunsubstituted fluorene ring and the substituted C6 to C30 aryl group maybe linked with an adjacent C1 to C30 alkenyl group to form atriphenylene ring, a naphthalene ring, a pyrazine ring, a quinazolinering, a quinoxaline ring, a phenanthroline ring, or the like.

In the present specification when specific definition is not otherwiseprovided, “hetero” refers to one including one to three heteroatomsselected from N, O, S, P, and Si, and remaining carbons in onefunctional group.

In the present specification, when a definition is not otherwiseprovided, “alkyl group” refers to an aliphatic hydrocarbon group. Thealkyl group may be “a saturated alkyl group” without any double bond ortriple bond.

The alkyl group may be a C1 to C30 alkyl group. More specifically, thealkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group.For example, a C1 to C4 alkyl group may have one to four carbon atoms inthe alkyl chain, and may be selected from methyl, ethyl, propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.

Specific examples of the alkyl group may be a methyl group, an ethylgroup, a propyl group, an isopropyl group, a butyl group, an isobutylgroup, a t-butyl group, a pentyl group, a hexyl group, a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, andthe like.

In the present specification, “an aryl group” refers to a groupincluding at least one hydrocarbon aromatic moiety, and

all elements of the hydrocarbon aromatic moiety have p-orbitals whichform conjugation, for example a phenyl group, a naphthyl group, and thelike,

two or more hydrocarbon aromatic moieties may be linked by a sigma bondand may be, for example a biphenyl group, a terphenyl group, aquarterphenyl group, and the like, and

two or more hydrocarbon aromatic moieties are fused directly orindirectly to provide a non-aromatic fused ring. For example, it may bea fluorenyl group.

The aryl group may include a monocyclic, polycyclic, or fused ringpolycyclic (i.e., rings sharing adjacent pairs of carbon atoms)functional group.

In the present specification, “a heterocyclic group” is a genericconcept of a heteroaryl group, and may include at least one heteroatomselected from N, O, S, P, and Si instead of carbon (C) in a cycliccompound such as an aryl group, a cycloalkyl group, a fused ringthereof, or a combination thereof. When the heterocyclic group is afused ring, the entire ring or each ring of the heterocyclic group mayinclude one or more heteroatoms.

For example, “a heteroaryl group” may refer to an aryl group includingat least one heteroatom selected from N, O, S, P, and Si instead ofcarbon (C). Two or more heteroaryl groups are linked by a sigma bonddirectly, or when the C2 to C60 heteroaryl group includes two or morerings, the two or more rings may be fused. When the heteroaryl group isa fused ring, each ring may include one to three heteroatoms.

Specific examples of the heteroaryl group may be a pyridinyl group, apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinylgroup, a quinolinyl group, an isoquinolinyl group, and the like.

More specifically, the substituted or unsubstituted C6 to C30 aryl groupand/or the substituted or unsubstituted C2 to C30 heterocyclic group maybe a substituted or unsubstituted phenyl group, a substituted orunsubstituted naphthyl group, a substituted or unsubstituted anthracenylgroup, a substituted or unsubstituted phenanthryl group, a substitutedor unsubstituted naphthacenyl group, a substituted or unsubstitutedpyrenyl group, a substituted or unsubstituted biphenyl group, asubstituted or unsubstituted p-terphenyl group, a substituted orunsubstituted m-terphenyl group, a substituted or unsubstitutedchrysenyl group, a substituted or unsubstituted triphenylenyl group, asubstituted or unsubstituted perylenyl group, a substituted orunsubstituted fluorenyl group, a substituted or unsubstituted indenylgroup, a substituted or unsubstituted furanyl group, a substituted orunsubstituted thiophenyl group, a substituted or unsubstituted pyrrolylgroup, a substituted or unsubstituted pyrazolyl group, a substituted orunsubstituted imidazolyl group, a substituted or unsubstituted triazolylgroup, a substituted or unsubstituted oxazolyl group, a substituted orunsubstituted thiazolyl group, a substituted or unsubstitutedoxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, asubstituted or unsubstituted pyridinyl group, a substituted orunsubstituted pyrimidinyl group, a substituted or unsubstitutedpyrazinyl group, a substituted or unsubstituted triazinyl group, asubstituted or unsubstituted benzofuranyl group, a substituted orunsubstituted benzothiophenyl group, a substituted or unsubstitutedbenzimidazolyl group, a substituted or unsubstituted indolyl group, asubstituted or unsubstituted quinolinyl group, a substituted orunsubstituted isoquinolinyl group, a substituted or unsubstitutedquinazolinyl group, a substituted or unsubstituted quinoxalinyl group, asubstituted or unsubstituted naphthyridinyl group, a substituted orunsubstituted benzoxazinyl group, a substituted or unsubstitutedbenzthiazinyl group, a substituted or unsubstituted acridinyl group, asubstituted or unsubstituted phenazinyl group, a substituted orunsubstituted phenothiazinyl group, a substituted or unsubstitutedphenoxazinyl group, a substituted or unsubstituted carbazolyl group, asubstituted or unsubstituted dibenzofuranyl group, a substituted orunsubstituted dibenzothiophenyl group, or a combination thereof, but arenot limited thereto.

In the present specification, a single bond refers to a direct bond notby carbon or a hetero atom except carbon, and specifically the meaningthat L is a single bond means that a substituent linked with L directlybonds with a central core. That is, in the present specification, thesingle bond does not refer to methylene that is bonded via carbon.

In the present specification, hole characteristics refer to an abilityto donate an electron to form a hole when an electric field is applied,and that a hole formed in the anode may be easily injected into thelight emitting layer, and a hole formed in a light emitting layer may beeasily transported into an anode and transported in the light emittinglayer due to conductive characteristics according to a highest occupiedmolecular orbital (HOMO) level.

In addition, electron characteristics refers to an ability to accept anelectron when an electric field is applied, and that an electron formedin a cathode may be easily injected into the light emitting layer, andan electron formed in a light emitting layer may be easily transportedinto a cathode and transported in the light emitting layer due toconductive characteristics according to a lowest unoccupied molecularorbital (LUMO) level.

Hereinafter, a composition for an organic optoelectronic deviceaccording to an embodiment is described.

A composition for an organic optoelectronic device according to anembodiment includes at least one first compound represented by formula 1and at least one second compound represented by formula 2.

In formula 1, X¹ to X¹² are independently N, C, or CR^(a), at least oneof X¹ to X⁶ is N, at least one of X⁷ to X¹² is N, R^(a)'s areindependently hydrogen, deuterium, a substituted or unsubstituted C1 toC30 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group,a substituted or unsubstituted C1 to C30 alkynyl group, a substituted orunsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 toC30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthiogroup, a substituted or unsubstituted C2 to C30 heteroaryl group, ahydroxyl group, a thiol group, or a combination thereof, R^(a)'s areindependently present or adjacent R^(a)'s are linked with each other toprovide a ring, and

L¹ is a C6 to C30 arylene group that is unsubstituted or substitutedwith deuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, or a C6 toC30 aryl group;

In formula 2,

L² to L⁴ are independently a single bond, a substituted or unsubstitutedC6 to C30 arylene group, or a substituted or unsubstituted C2 to C30heteroarylene group,

Ar¹ to Ar³ are independently, a substituted or unsubstituted C6 to C30aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group,or a combination thereof, and

when specific definition is not otherwise provided, “substituted” offormulas 1 and 2 refers to replacement of at least one hydrogen bydeuterium, a halogen, a hydroxyl group, an amino group, a C1 to C30amine group, a C6 to C30 arylamine group, a nitro group, a C1 to C40silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkylgroup, or a cyano group.

A composition for an organic optoelectronic device according to oneembodiment of the present invention uses a first compound including acompound in which nitrogen-containing heterorings are linked through anarylene linker and thus having excellent electron injection andtransport characteristics and a second compound including at least oneamine group substituted with at least one aryl group and/or heteroarylgroup and thus having excellent hole injection and transportcharacteristics to form an light emitting layer and resultantly, maylower a driving voltage and simultaneously realize an organic lightemitting diode having a long life-span and high efficiency.

The first compound respectively includes at least onenitrogen-containing ring in substituents positioned at both ends of thelinking group, L¹ and thus has a structure of easily accepting anelectron when an electric field is applied and thus may increase theinjection amount of electrons and have relatively strong electrontransport characteristics.

In particular, various characteristics such as charge injectioncharacteristics, a deposition temperature, a glass transitiontemperature, and the like may be adjusted depending on the number of Nincluded in the substituents at both ends, a linking direction of thelinking group, L¹, the number of an arylene group linked thereby, andthe like.

Accordingly, the first compound may lower a driving voltage of anorganic optoelectronic device and also, improve its efficiency.

Formula 1 according to an example embodiment of the present inventionmay be, for example represented by one of formula 1-I to formula 1-IV inaccordance with that adjacent R^(a)'s are linked to each other to form aring.

In formulas 1-I to 1-IV, L¹ is the same described above, Z's areindependently N or CR^(a), wherein R^(a) is the same as described above,and in each ring including Z, at least one Z may be N.

Various characteristics such as charge injection characteristics, adeposition temperature, a glass transition temperature, and the like maybe adjusted depending on the number of N included in a substituent atboth ends. Specifically, when the entire number of the N is greater thanor equal to 4, electron injection characteristics may be stronger. Forexample, the number of the N may be respectively (1 and 3), (2 and 2),(2 and 3), or (3 and 3) and in particular, when the number of the N is(3 and 3), stability and mobility of injected electrons may beparticularly improved.

In an exemplary embodiment of the present invention, R^(a), R^(a1) toR^(a4), R^(c), R^(d), R^(e), R^(f), R^(g), and R^(h) are independentlyhydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkylgroup, a substituted or unsubstituted C6 to C30 aryl group, asubstituted or unsubstituted C2 to C30 heteroaryl group, or acombination thereof,

specifically, hydrogen or a substituted or unsubstituted C6 to C30 arylgroup, and

more specifically hydrogen, a substituted or unsubstituted phenyl group,a substituted or unsubstituted biphenyl group, a substituted orunsubstituted terphenyl group, a substituted or unsubstitutedquaterphenyl group, a substituted or unsubstituted naphthyl group, asubstituted or unsubstituted anthracenyl group, a substituted orunsubstituted triphenylene group, a substituted or unsubstitutedphenanthrenyl group, or a substituted or unsubstituted pyrenyl group.

For example, they may be substituted with deuterium, a C1 to C10 alkylgroup, a C6 to C12 aryl group or they may be selected from the followingunsubstituted groups of Group 1, but are not limited thereto.

[Group 1]

In Group 1, * is a linking point.

On the other hand, in another embodiment of the present invention, theadjacent R^(a)'s may be linked to each other to form a ring, wherein thering formed by linking the R^(a)'s may be a substituted or unsubstitutedquinolinyl group, a substituted or unsubstituted isoquinolinyl group, asubstituted or unsubstituted quinolinyl group quinazolinyl group, or asubstituted or unsubstituted phenanthrolinyl group.

Specifically, R^(a)'s are independently present to be a substituted orunsubstituted pyridinyl group, or a substituted or unsubstitutedtriazinyl group, or

the adjacent R^(a)'s are linked with each other to provide a substitutedor unsubstituted quinazolinyl group.

L¹ of formula 1 according to an example embodiment of the presentinvention may be specifically a phenylene group that is unsubstituted orsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkylgroup, or a C6 to C30 aryl group; a biphenylene group that isunsubstituted or substituted with deuterium, a C1 to C40 silyl group, aC1 to C30 alkyl group, or a C6 to C30 aryl group; a terphenylene groupthat is unsubstituted or substituted with deuterium, a C1 to C40 silylgroup, a C1 to C30 alkyl group, or a C6 to C30 aryl group; or aquarterphenylene group that is unsubstituted or substituted withdeuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 toC30 aryl group.

Particularly, various characteristics such as charge injectioncharacteristics, a deposition temperature, a glass transitiontemperature, and the like may be adjusted depending on a linkingdirection of a linking group, L¹ and the number of an arylene grouplinked therewith, and the linking group, L¹ may be for example, selectedfrom substituted or unsubstituted linking groups provided in Group 2 butis not limited thereto.

[Group 2]

In Group 2, * is a linking point with an adjacent atom. When the L¹ isthe same as above, formula 1 may be a dimer including two N-containingheterorings, this dimer may easily adjust hole mobility and electronmobility characteristics depending on characteristics of a substituentand thus suppress formation of a crystalline phase compared with atrimer including three N-containing heterorings.

In particular, as a ratio of a moiety linked at a para position in theL¹ increases, a molecule itself becomes firm and thus may increasecharge mobility.

In addition, a deposition temperature and a glass transition temperaturemay be adjusted by controlling ratios of moieties linked as a meta orortho position in the L¹.

Particularly, a LUMO energy level and thus charge injectioncharacteristics may be adjusted by controlling the number of aryl groupincluded in the L¹ and a kind of and a direction of substituentsincluded in the heterorings.

In an example embodiment of the present invention, in formula 1, X¹ toX¹² are independently N, C, or CR^(a), at least two of X¹ to X⁶ are N,at least two of X⁷ to X¹² are N, R^(a)'s are independently hydrogen,deuterium, a substituted or unsubstituted C1 to C30 alkyl group, asubstituted or unsubstituted C6 to C30 aryl group, a substituted orunsubstituted C2 to C30 heteroaryl group, or a combination thereof, andL¹ is a C6 to C30 arylene group that is unsubstituted or substitutedwith deuterium, a C1 to C30 alkyl group, or a C6 to C30 aryl group, and

more specifically, a heterocyclic group composed of X¹ to X⁶ may be apyrimidinyl group or a triazinyl group and a heterocyclic group composedof X⁷ to X¹² may be a pyrimidinyl group or a triazinyl group.

For example, X¹ to X¹² of formula 1 may independently be N, C, orCR^(a), three of X¹ to X⁶ may be N, and three of X⁷ to X¹² may be N. Forexample, the heterocyclic group consisting of X¹ to X⁶ and theheterocyclic group consisting of X⁷ to X¹² may be a triazinyl group.

Herein, when specific definition is not otherwise provided,“substituted” refers to replacement of at least one hydrogen bydeuterium, a halogen, a hydroxyl group, a C1 to C40 silyl group, a C1 toC30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30heterocycloalkyl group, a C6 to C30 aryl group, or a C2 to C30heterocyclic group.

Specifically, R^(a)'s may be a substituted or unsubstituted C6 to C30aryl group, and

the C6 to C30 aryl group may be a substituted or unsubstituted phenylgroup, a substituted or unsubstituted biphenyl group, a substituted orunsubstituted terphenyl group, a substituted or unsubstitutedquaterphenyl group, a substituted or unsubstituted naphthyl group, asubstituted or unsubstituted anthracenyl group, a substituted orunsubstituted fluorenyl group, a substituted or unsubstitutedtriphenylene group, or a substituted or unsubstituted phenanthrenylgroup. In addition, for example, in “substituted or unsubstituted” ofR^(a)'s, “substituted” may be deuterium, a C1 to C10 alkyl group, a C6to 20 aryl group, or a pyrimidine group.

The first compound represented by formula 1 may be for example compoundsof Group 3, but is not limited thereto.

[Group 3]

The first compound used in a light emitting layer has strong electrontransport and inject characteristics, and thus crystallinity of amaterial may be increased.

Accordingly, the first compound may be used with a material havingstrong hole transport and injection characteristics rather than usedalone to balance hole transport and injection characteristics/electrontransport and injection characteristics.

The compound having strong hole transport and injection characteristicsmay be a second compound represented by formula 2.

The second compound is a compound having relatively strong holecharacteristics due to the amine group substituted with at least onearyl group and/or heteroaryl group and is used in a light emitting layerwith the first compound to increase charge mobility and stability andthereby to remarkably improve luminous efficiency and life-spancharacteristics.

L² to L⁴ of formula 2 may independently be a single bond, a substitutedor unsubstituted C6 to C30 arylene group, or a substituted orunsubstituted C2 to C30 heteroarylene group,

for example, a single bond, a substituted or unsubstituted phenylenegroup, a substituted or unsubstituted biphenylene group, a substitutedor unsubstituted naphthyl group, a substituted or unsubstitutedfluorenyl group, a substituted or unsubstituted pyridinyl group, asubstituted or unsubstituted pyrimidinyl group, a substituted orunsubstituted quinolinyl group, or a combination thereof.

In addition, Ar¹ to Ar³ of formula 2 may independently be a substitutedor unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2to C30 heterocyclic group, or a combination thereof,

more specifically, a substituted or unsubstituted phenyl group, asubstituted or unsubstituted biphenyl group, a substituted orunsubstituted terphenyl group, a substituted or unsubstitutedquaterphenyl group, a substituted or unsubstituted naphthyl group, asubstituted or unsubstituted fluorenyl group, a substituted orunsubstituted carbazolyl group, a substituted or unsubstituteddibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylgroup, a substituted or unsubstituted anthracenyl group, a substitutedor unsubstituted phenanthrenyl group, a substituted or unsubstitutedtriphenylene group, a substituted or unsubstituted quinolinyl group, asubstituted or unsubstituted pyridinyl group, a substituted orunsubstituted pyrimidinyl group, a substituted or unsubstitutedthiophenyl group, or a combination thereof.

For example, Ar¹ to Ar³ may independently be selected from substitutedor unsubstituted groups of Group 4.

[Group 4]

In Group 4, * is a linking point with an adjacent atom.

Ar¹ to Ar³ of formula 2 according to an example embodiment of thepresent invention may be further substituted with a C6 to C30 arylgroup, or a C1 to C30 alkyl group or the substituents may be linked witheach other to form a fused ring.

For example, when the substituents of Ar¹ to Ar³ are a triphenylmethylgroup, two adjacent phenyl group to the triphenylmethyl group may belinked to form a fluorene ring.

The second compound represented by formula 2 may be, for examplecompounds of Group 5, but is not limited thereto.

[Group 5]

On the other hand, charge mobility may be adjusted by controlling aratio between the second compound having hole characteristics and thefirst compound.

A HOMO energy level of the second compound may be −4.6 eV to −5.5 eV anda LUMO energy level thereof may be −1.7 eV to −0.850 eV.

In addition, the first compound and the second compound may be includedfor example in a weight ratio of about 1:9 to 9:1, specifically, 2:8 to8:2, 3:7 to 7:3, 4:6 to 6:4, and 5:5. Within the ranges, bipolarcharacteristics may be further effectively realized, and thus efficiencyand life-span may be simultaneously improved.

Specifically, in the light emitting layer 130, the first compound andthe second compound may be simultaneously included as a host, forexample the first compound may be represented by formula 1-Ia or formula1-IVa and the second compound may be formula 2 wherein L² to L⁴ areindependently a single bond, or a substituted or unsubstituted phenylenegroup, and Ar¹ to Ar³ are independently a substituted or unsubstitutedC6 to C30 aryl group, or a substituted or unsubstituted C2 to C30heterocyclic group, provided that at least one of Ar¹ to Ar³ is asubstituted or unsubstituted C2 to C30 heterocyclic group.

In formulas 1-Ia and 1-IVa, Z¹ to Z⁶ are independently N, or CR^(a), atleast two of Z¹ to Z³ are N, at least two of Z⁴ to Z⁶ are N, R^(a), andR^(a)t to R^(a4) are independently hydrogen, or a substituted orunsubstituted C6 to C30 aryl group, and L¹ is a C6 to C30 arylene groupthat is unsubstituted or substituted with deuterium, a C1 to C30 alkylgroup, or a C6 to C30 aryl group;

wherein, “substituted” is the same as described above.

More specifically, the first compound may be represented by formula1-Ia-1 or formula 1-IVa-1 and the second compound may be represented byformula 2 wherein Ar¹ to Ar³ are independently a substituted orunsubstituted phenyl group, a substituted or unsubstituted biphenylgroup, a substituted or unsubstituted terphenyl group, a substituted orunsubstituted naphthyl group, a substituted or unsubstitutedphenanthrenyl group, a substituted or unsubstituted carbazolyl group, asubstituted or unsubstituted dibenzofuranyl group, or a substituted orunsubstituted dibenzothiophenyl group, provided that at least one of Ar¹to Ar³ is a substituted or unsubstituted carbazolyl group, a substitutedor unsubstituted dibenzofuranyl group, or a substituted or unsubstituteddibenzothiophenyl group.

In formula 1-Ia-1 and formula 1-IVa-1, R^(a1) to R^(a4), L¹, R^(c),R^(f), and “substituted” are the same as described above.

The light emitting layer 130 may further include at least one compoundin addition to the first compound and the second compound as a host. Forexample, aryl amine compound or aryl amine carbazole compound havingexcellent hole characteristics may be further included.

The light emitting layer 130 may further include a dopant. The dopant ismixed with a host in a small amount to cause light emission, and may begenerally a material such as a metal complex that emits light bymultiple excitation into a triplet or more. The dopant may be, forexample an inorganic, organic, or organic/inorganic compound, and one ormore kinds thereof may be used.

The dopant may be a red, green, or blue dopant, for examplephosphorescent dopant. Examples of the phosphorescent dopant may be anorganic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe,Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopantmay be, for example a compound represented by formula Z, but is notlimited thereto.

L₂MX  [formula Z]

In formula Z, M is a metal, and L and X are the same or different, andare a ligand to form a complex compound with M.

The M may be for example Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni,Ru, Rh, Pd or a combination thereof, and the L and X may be, for examplea bidendate ligand.

The composition may be applied to an organic layer of an organicoptoelectronic device, for example a light emitting layer. For example,the composition may be applied to a light emitting layer as a host.

The composition may be formed using a dry film formation method or asolution process. The dry film formation method may be, for example achemical vapor deposition (CVD) method, sputtering, plasma plating, andion plating, and two or more compounds may be simultaneously formed intoa film or compound having the same deposition temperature may be mixedand formed into a film. The solution process may be, for example inkjetprinting, spin coating, slit coating, bar coating and/or dip coating.

Hereinafter, an organic optoelectronic device including the compositionis described.

The organic optoelectronic device may be any device to convertelectrical energy into photoenergy and vice versa without particularlimitation, and may be selected from an organic light emitting diode, anorganic photoelectric device, an organic solar cell, an organictransistor, an organic photo conductor drum, and an organic memorydevice.

The organic optoelectronic device includes an anode and a cathode facingeach other, and at least one organic layer interposed between the anodeand the cathode, wherein the organic layer includes the composition.

Herein, an organic light emitting diode as one example of an organicoptoelectronic device is described referring to drawings.

FIG. 1 is a schematic cross-sectional view of an organic light emittingdiode according to an embodiment.

Referring to FIG. 1, an organic light emitting diode 100 according to anembodiment includes an anode 120 and a cathode 110 facing each other andan organic layer 105 between the anode 120 and the cathode 110.

The anode 120 may be made of a conductor having a large work function tohelp hole injection, and may be for example made of a metal, a metaloxide, and/or a conductive polymer. The anode 120 may be, for example ametal such as nickel, platinum, vanadium, chromium, copper, zinc, andgold or an alloy thereof; metal oxide such as zinc oxide, indium oxide,indium tin oxide (ITO), indium zinc oxide (IZO), and the like; acombination of metal and oxide such as ZnO and Al or SnO₂ and Sb; aconductive polymer such as poly(3-methylthiophene),poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, andpolyaniline, but is not limited thereto.

The cathode 110 may be made of a conductor having a small work functionto help electron injection, and may be for example made of a metal, ametal oxide and/or a conductive polymer. The cathode 110 may be forexample a metal or an alloy thereof such as magnesium, calcium, sodium,potassium, titanium, indium, yttrium, lithium, gadolinium, aluminumsilver, tin, lead, cesium, barium, and the like; a multi-layer structurematerial such as LiF/Al, LiO₂/Al, LiF/Ca, LiF/Al and BaF₂/Ca, but is notlimited thereto.

The organic layer 105 includes a light emitting layer 130 including thecomposition.

FIG. 2 is a cross-sectional view showing an organic light emitting diodeaccording to another embodiment.

Referring to FIG. 2, an organic light emitting diode 200 according tothe present embodiment includes an anode 120 and a cathode 110 facingeach other and an organic layer 105 between the anode 120 and thecathode 110 like the above embodiment.

The organic layer 105 includes a light emitting layer 130 and anauxiliary layer 140 between the light emitting layer 130 and the anode120. The auxiliary layer 140 may help charge injection and transferbetween the anode 120 and the light emitting layer 130. The auxiliarylayer 140 may be, for example a hole transport layer (HTL), a holeinjection layer (HIL), and/or an electron blocking layer, and mayinclude at least one layer.

In FIGS. 1 and 2, at least one auxiliary layer between the cathode 110and the light emitting layer 130 may be further included as an organiclayer 105. The auxiliary layer may be, for example an electron transportlayer (ETL), an electron injection layer (EIL), and/or an electrontransport auxiliary layer.

The organic light emitting diode may be applied to an organic lightemitting display device.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. These examples, however, are not in any sense tobe interpreted as limiting the scope of the invention.

MODE FOR INVENTION

Hereinafter, a starting material and a reactant used in SynthesisExamples and Examples were purchased from Sigma-Aldrich Corporation orTCI Inc. unless there was particularly mentioned.

Synthesis of First Compound Synthesis Example 1: Synthesis of Compound 1a) Synthesis of Intermediate 1-1

20 g (51.51 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine wasdissolved in 250 mL of toluene in a 500 mL round-bottomed flask. Then,0.05 equivalent of dichlorodiphenylphosphinoferrocene palladium, 1.2equivalent of bis(pinacolato)diboron, and 2 equivalents of potassiumacetate were added thereto, and the mixture was heated and refluxedunder a nitrogen atmosphere for 18 hours. The reaction solution wascooled down, 100 mL of water was added thereto, and an organic layer wasextracted therefrom. The organic layer was collected, treated withactivated carbon, and filtered through silica gel, and the filteredsolution was concentrated. The concentrated residue was collected andthen, crystallized in 200 mL of toluene and 50 mL of acetone to obtain19.1 g of Intermediate 1-1.

b) Synthesis of Compound 1

19 g (43.79 mmol) of the synthesized Intermediate 1-1 was added to 200mL of tetrahydrofuran and 50 mL of distilled water in a 500 mLround-bottomed flask, 1 equivalent of2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 0.03 equivalent oftetrakistriphenylphosphine palladium, and 2 equivalents of potassiumcarbonate were added thereto, and the mixture was heated and refluxedunder a nitrogen atmosphere. After 18 hours, the reaction solution wascooled down, and a solid precipitated therein was filtered and washedwith 500 mL. The solid was recrystallized with 500 mL ofmonochlorobenzene to obtain 22.41 g of Compound 1.

LC/MS calculated for: C₄₂H₂₈N₆ Exact Mass: 616.2375 found for: 617.24[M+H].

Synthesis Example 2: Synthesis of Compound 2

15 g (34.46 mmol) of the synthesized Intermediate 1-1, 0.5 equivalent of1,3-dibromobenzene, 0.03 equivalent of tetrakistriphenylphosphinepalladium, 2 equivalents of potassium carbonate, 200 mL oftetrahydrofuran, and 50 mL of distilled water were put in a 500 mLround-bottomed flask and then, heated and refluxed under a nitrogenatmosphere. After 20 hours, the reaction solution was cooled down, and asolid precipitated therein was filtered and washed with 500 mL of water.The solid was recrystallized with 400 mL of dichlorobenzene to obtain9.2 g of Compound 2.

LC/MS calculated for: C₄₈H₃₂N₆ Exact Mass: 692.2688 found for: 693.27[M+H].

Synthesis Example 3: Synthesis of Compound 3 a) Synthesis ofIntermediate 3-1

30 g (68.92 mmol) of the synthesized Intermediate 1-1, 1.2 equivalent of1,3-dibromobenzene, 0.03 equivalent of tetrakistriphenylphosphinepalladium, 2 equivalents of potassium carbonate, 300 mL oftetrahydrofuran, and 100 mL of distilled water were put in a 500 mLround-bottomed flask and then, heated and refluxed under a nitrogenatmosphere. After 18 hours, the reaction solution was cooled down,suspended in 1 L of methanol, stirred, filtered, and washed with 500 mLof water. Then, a solid therein was recrystallized with 400 mL ofdichlorobenzene to obtain 32 g of Intermediate 3-1.

b) Synthesis of Intermediate 3-2

32 g (68.91 mmol) of the synthesized Intermediate 3-1 was reactedaccording to the same method as in a) the synthesis method ofIntermediate 1-1 in Synthesis Example 1 in a 500 mL round-bottomed flaskto obtain 29.96 g of Intermediate 3-2.

c) Synthesis of Compound 3

15 g (29.33 mmol) of the synthesized Intermediate 3-2, 1 equivalent ofthe synthesized Intermediate 3-1, 0.03 equivalent oftetrakistriphenylphosphine palladium, 2 equivalents of potassiumcarbonate, 200 mL of tetrahydrofuran, an 50 mL of distilled water wereput in a 500 mL round-bottomed flask and then, heated and refluxed undera nitrogen atmosphere. After 18 hours, the reaction solution was cooleddown, filtered, and washed with 500 mL of water. Then, a solid thereinwas recrystallized with 500 mL of dichlorobenzene to obtain 16.01 g ofCompound 3.

LC/MS calculated for: C₅₄H₃₆N₆ Exact Mass: 768.3001 found for: 769.3[M+H].

Synthesis Example 4: Synthesis of Compound 100 a) Synthesis ofIntermediate Intermediate 100-1

15 g (29.33 mmol) of the synthesized Intermediate 3-2 was reactedaccording to the same method as in a) the synthesis method ofIntermediate 3-1 in Synthesis Example 3 in a 500 mL round-bottomed flaskto obtain 12.84 g of Intermediate 100-1.

b) Synthesis of Compound 100

12 g (22.2 mmol) of the synthesized Intermediate 100-1, 1.2 equivalentof the synthesized Intermediate 3-2, 0.03 equivalent oftetrakistriphenylphosphine palladium, 2 equivalent of potassiumcarbonate, 150 mL of tetrahydrofuran, and 50 mL of distilled water wereput in a 500 mL round-bottomed flask and then, heated and refluxed undera nitrogen atmosphere. After 18 hours, the reaction solution was cooleddown, suspended in 1 L of methanol, stirred and filtered, and then,washed with 500 mL of water. Then, a solid therefrom is recrystallizedwith 500 mL of dichlorobenzene to obtain 13.3 g of Compound 100.

LC/MS calculated for: C₆₀H₄₀N₆ Exact Mass: 844.3314 found for 845.34[M+H].

Synthesis Example 5: Synthesis of Compound 4 a) Synthesis ofIntermediate 4-2

15 g (81.34 mmol) of cyaburic chloride was dissolved in 200 mL ofanhydrous tetrahydrofuran in a 500 mL round-bottomed flask, 1 equivalentof a 4-biphenyl magnesium bromide solution (0.5 M tetrahydrofuran) wasadded thereto in a dropwise fashion under a nitrogen atmosphere at 0°C., and the mixture was slowly heated up to room temperature. Then, thereaction solution was stirred at room temperature for 1 hour, stirred,and then, poured into 500 mL of ice water to separate a layer. Theseparated organic layer was treated with anhydrous magnesium sulfate andconcentrated. The concentrated residue was recrystallized withtetrahydrofuran and methanol to obtain 17.2 g of Intermediate 4-2.

b) Synthesis of Intermediate 4-1

17 g (56.26 mmol) of the synthesized Intermediate 4-2 was put in a 500mL round-bottomed flask, 1 equivalent of phenylboronic acid, 0.03equivalent of tetrakistriphenylphosphine palladium, 2 equivalents ofpotassium carbonate, 150 mL of tetrahydrofuran, and 50 mL of distilledwater were added thereto, and the mixture was heated and refluxed undera nitrogen atmosphere. After 18 hours, the reaction solution was cooleddown, suspended in 1 L of methanol, stirred and filtered, washed with500 mL of water, and dried to obtain 12.57 g of Intermediate 4-1.

c) Synthesis of Compound 4

12 g (34.9 mmol) of the synthesized Intermediate 4-1 was put in a 500 mLround-bottomed flask, 1.1 equivalent of the synthesized Intermediate3-2, 0.03 equivalent of tetrakistriphenylphosphine palladium, 2equivalents of potassium carbonate, 150 mL of tetrahydrofuran, and 50 mLof distilled water were added thereto, and the mixture was heated andrefluxed under a nitrogen atmosphere. After 18 hours, the reactionsolution was cooled down, suspended in 1 L of methanol, stirred andfiltered, and washed with 500 mL of water. Then, a solid producedtherein was recrystallized with 500 mL of dichlorobenzene to obtain 17.8g of Compound 4.

LC/MS calculated for: C₄₈H₃₂N₆ Exact Mass: 692.2688 found for 692.27[M+H].

Synthesis Example 6: Synthesis of Compound 16 a) Synthesis ofIntermediate 16-2

Intermediate 16-2 was synthesized according to the same method as a) thesynthesis of Intermediate 4-2 of Synthesis Example 5 by using a3-biphenyl magnesium bromide solution (0.5 M tetrahydrofuran) instead ofthe 4-biphenyl magnesium bromide solution (0.5 M tetrahydrofuran).

b) Synthesis of Intermediate 16-1

Intermediate 16-1 was synthesized according to the same method as b) themethod of Synthesis Example 5 by using Intermediate 16-2 instead ofIntermediate 4-2.

c) Synthesis of Compound 16

Compound 16 was synthesized according to the same method as c) themethod of Synthesis Example 5.

LC/MS calculated for: C₄₈H₃₂N₆ Exact Mass: 692.2688 found for 692.27[M+H].

Synthesis Example 7: Synthesis of Compound 126

Compound 126 was synthesized according to the same method as SynthesisExample 2 by using 1,2-dibromobenzene as an intermediate.

LC/MS calculated for: C₄₈H₃₂N₆ Exact Mass: 692.2688, found for 693.28[M+H].

Synthesis Example 8: Synthesis of Compound 140 a) Synthesis ofIntermediate 140-1

20 g (39.11 mmol) of Intermediate 3-2 was put in a 500 mL round-bottomedflask, 1.1 equivalent of 1,2-dibromobenzene, 0.03 equivalent oftetrakistriphenylphosphine palladium, 2 equivalents of potassiumcarbonate, 200 mL of tetrahydrofuran, and 50 mL of distilled water wereadded thereto, and the mixture was heated and refluxed under a nitrogenatmosphere. After 18 hours, the reaction solution was cooled down,suspended in 500 mL of methanol, stirred and filtered, and washed with500 mL of water. Then, a solid produced therein was recrystallized with500 mL of monochlorobenzene to obtain 18.4 g of Intermediate 140-1.

b) Synthesis of Compound 140

18 g (33.31 mmol) of the synthesized Intermediate 140-1 was put in a 500mL round-bottomed flask, 1.1 equivalent of the synthesized Intermediate1-1, 0.03 equivalent of tetrakistriphenylphosphine palladium, 2equivalents of potassium carbonate, 200 mL of tetrahydrofuran, and 50 mLof distilled water were added thereto, and the mixture was heated andrefluxed under a nitrogen atmosphere. After 18 hours, the reactionsolution was cooled down, suspended in 500 mL of methanol, stirred andfiltered, and washed with 500 mL of water. Then, a solid obtainedtherein was collected, silica gel column purified with a mixed solventof normal hexane and ethyl acetate to obtain 19.2 g of Compound 140.

LC/MS calculated for: C₅₄H₃₆N₆ Exact Mass: 768.3001, found for 769.3[M+H].

Synthesis Example 9: Synthesis of Compound 113 a) Synthesis ofIntermediate 113-3

30 g (168.37 mmol) of methyl benzoyl acetate was put in a 500 mLround-bottomed flask, 1.1 equivalent of 3-chlorophenyl amidine, 1.2equivalent of sodium methoxide, and 200 mL of methanol were addedthereto, and the mixture heated and refluxed for 6 hours. The reactionsolution was cooled down, a 1 N hydrochloric acid solution was addedthereto, and chloridemethane was used for an extraction. The extractedsolution was concentrated to obtain Intermediate 113-4, which itself isused for the following reaction.

Intermediate 113-4 was put in a 500 mL round-bottomed flask, 250 mL ofphosphorylchloride was added thereto, and the mixture was heated andrefluxed for 5 hours. The reaction solution was cooled down and slowlyadded to 1 L of ice water, and the mixture is stirred. Then, an aqueouslayer is extracted with 500 mL of methane chloride, dried with anhydrousmagnesium sulfate, and concentrated. The concentrated residue waspurified through a silica gel column by using normal hexane and ethylacetate to obtain 39 g of Intermediate 113-3.

b) Synthesis of Intermediate 113-2

30 g (99.6 mmol) of the synthesized Intermediate 113-3 was put in a 500mL round-bottomed flask, 1.2 equivalent of biphenyl boronic acid, 0.03equivalent of tetrakistriphenylphosphine palladium, 2 equivalents ofpotassium carbonate, 250 mL of tetrahydrofuran, and 70 mL of distilledwater were added thereto, and the mixture was heated and refluxed undera nitrogen atmosphere. After 18 hours, the reaction solution was cooleddown, suspended in 500 mL of methanol, stirred and filtered, and washedwith 500 mL of water. Then, a solid produced therein was collected andthen, heated and recrystallized with 500 mL of toluene to obtain 35.9 gof Intermediate 113-2.

c) Synthesis of Intermediate 113-1

35 g (83.5 mmol) of the synthesized Intermediate 113-2 was put in a 500mL round-bottomed flask, 250 mL of toluene, 0.05 equivalent ofdichlorodiphenylphosphinoferrocene 1.2 equivalent ofbis(pinacolato)diboron palladium, and 2 equivalents of potassium acetatewere added thereto, and the mixture was heated and refluxed for 18 hoursunder a nitrogen atmosphere. The reaction solution was cooled down, and100 mL of water was added thereto to extract an organic layer. Theorganic layer was collected, treated with activated carbon, filteredthrough silica gel, and concentrated. The concentrated residue wascollected, heated and dissolved in 1 L of toluene, treated withactivated carbon, filtered through silica gel. The filtered solution wascooled down and stirred to precipitate a solid. The precipitated solidwas filtered to obtain 35.8 g of Intermediate 113-1.

d) Synthesis of Compound 113

35 g (68.6 mmol) of the synthesized Intermediate 113-1, 1 equivalent of2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 0.03 equivalent oftetrakistriphenylphosphine palladium, 2 equivalents of potassiumcarbonate, 250 mL of tetrahydrofuran, and 70 mL of distilled water wereput in a 500 mL round-bottomed flask and then, heated and refluxed undera nitrogen atmosphere. After 16 hours, the reaction solution was cooleddown, suspended in 500 mL of methanol, stirred and filtered, and washedwith 500 mL of water. Then, a solid produced therein was collected andthen, heated and recrystallized with 500 mL of dichlorobenzene to obtain32 g of Compound 113.

LC/MS calculated for: C₄₉H₃₃N₅ Exact Mass: 691.2736, found for: 692.29[M+H].

Synthesis Example Ad-1: Synthesis of Compound 181 a) Synthesis ofIntermediate q-3

1 equivalent of 2,4-dichloro quinazoline, 1.1 equivalents of 4-biphenylboronic acid, 0.03 equivalents of tetrakistriphenyl phosphine, and 3equivalents of potassium carbonate were heated and refluxed in asolution of tetrahydrofuran and water (3:1) in a round-bottomed flask tobe 0.25 M for 19 hours. The reaction solution was cooled down to roomtemperature and an organic layer was separated and concentrated. Theconcentrated residue was recrystallized with a mixed solution of normalhexane and dichloromethane to obtain 15 g of Intermediate q-3 (yield75%).

LC-Mass (theoretical value: 316.08 g/mol, measured value: M+1=317 g/mol)

b) Synthesis of Intermediate q-2

1 equivalent of the synthesized Intermediate q-3, 1.2 equivalents of2-chlorophenyl boronic acid, 0.03 equivalent of tetrakistriphenylphosphine, and 3 equivalents of potassium carbonate were heated andrefluxed in a solution of tetrahydrofuran and water (3:1) to be 0.25 Mfor 18 hours. The reaction solution was cooled down to room temperature,was diluted in methanol to be 0.1 M, and then was stirred to precipitatea solid. The produced solid was filtered and recrystallized with ethylacetate to obtain Intermediate q-2 21 g (yield 89%).

LC-Mass (theoretical value: 316.08 g/mol, measured value: M+1=317 g/mol)

c) Synthesis of Intermediate q-1

15 g of Intermediate q-1 was obtained according to the same method asthe synthesis method of Intermediate 1-1 or Intermediate 3-2 except forusing 1 equivalent of the synthesized Intermediate q-2 (yield 75%).

LC-Mass (theoretical value: 484.23 g/mol, measured value: M+1=485. 27g/mol)

d) Synthesis of Compound 181

1 equivalent of the synthesized Intermediate q-1 and 1 equivalent ofIntermediate q-2 were put in a round flask, 0.03 equivalent ofbisdibenzylidine palladium, 0.06 equivalent of tristertiary butylphosphine, and 2 equivalents of cecium carbonate were suspended in a1,4-dioxane solvent to be 0.25 M, and and the mixture was heated andrefluxed under a nitrogen atmosphere for 20 hours. The solid producedduring the reaction was filtered and washed with water and dried. Thedried solid was heated and recrystallized in 0.1 M of dichlorobenzene toobtain Compound 181 11 g (yield 72%) LC-Mass (theoretical value: 714.28g/mol, measured value: M+1=715.31 g/mol)

Synthesis Example Ad-2: Synthesis of Compound 180

Compound 180 was synthesized using “phenyl boronic acid” instead of“4-biphenyl boronic acid” in a) the synthesis of Intermediate q-3 ofSynthesis Example Ad-1 and using the synthesis method of SynthesisExample Ad-1.

LC-Mass (theoretical value: 638.76 g/mol, measured value: M+1=639.80g/mol)

Synthesis Example Ad-3: Synthesis of Compound 183

Compound 183 was synthesized using “phenyl boronic acid” instead of“4-biphenyl boronic acid” in a) the synthesis of Intermediate q-3 ofSynthesis Example Ad-1 and using the synthesis method of SynthesisExample Ad-1.

LC-Mass (theoretical value: 562.66 g/mol, measured value: M+1=563.69g/mol)

Synthesis Example Ad-4: Synthesis of Compound 190

Compound 190 was synthesized using “phenyl boronic acid” instead of“4-biphenyl boronic acid” in a) the synthesis of Intermediate q-3 ofSynthesis Example Ad-1, using “2-chloro-2′-biphenyl boronic acid”instead of “2-chlorophenyl boronic acid” in b) step, and using thesynthesis method of Synthesis Example Ad-1.

LC-Mass (theoretical value: 638.76 g/mol, measured value: M+1=639.77g/mol)

Synthesis of Second Compound Synthesis of Intermediate M-1

50 g (155.18 mmol) of 3-bromo-9-phenyl-9H-carbazole, 3.41 g (4.65 mmol)of Pd(dppf)C₂, 51.32 g (201.8 mmol) of bis(pinacolato)diboron, and 45.8g (465.5 mmol) of potassium acetate were dissolved in 520 ml of1,4-dioxane. The reactant was refluxed and stirred for 12 hours under anitrogen atmosphere and then extracted for 3 times with dichloromethaneand distilled water. The extracted solution was dried with magnesiumsulfite and filtered, and the filtrate was concentrated under a reducedpressure. The product was purified with n-hexane/dichloromethane (7:3volume ratio) through a silica gel column chromatography to obtain 43 g(yield 75%) of white solid Intermediate M-1 as a target compound.

LC-Mass (theoretical value: 369.19 g/mol, measured value: M+1=370 g/mol)

Synthesis of Intermediate M-2

40 g (108.3 mmol) of Intermediate M-1, 30.6 g (108.3 mmol) of1-bromo-4-iodobenzene and 1.25 g (1.08 mmol) oftetrakistriphenylphosphine palladium were added in a flask and dissolvedin 270 ml of toluene and 135 ml of ethanol under a nitrogen atmosphere.

Then, 135 ml of an aqueous solution including 31.9 g (58.9 mmol) ofpotassium carbonate was added into the reactants and then refluxed andstirred for 12 hours. After the reaction, the reactants were extractedwith ethylacetate, the extract was dried with magnesium sulfite andfiltered, and then, the filtrate was concentrated under reducedpressure. The product was purified with n-hexane/dichloromethane (7:3volume ratio) through a silica gel column chromatography and then 35 gof white solid Intermediate M-2 was obtained as a target compound (yield81%).

LC-Mass (theoretical value: 398.29 g/mol, measured value: M+1=399 g/mol)

Synthesis of Intermediate M-3

10 g (59.5 mmol) of a dibenzofuran was added in a two neckround-bottomed flask that was dried under vacuum and 119 mL of anhydroustetrahydrofuran was added under a nitrogen atmosphere followed bydissolving, and then, being cooling down to −40° C. and stirred.

Then, 26 mL of 2.5 M n-butyl lithium (in hexane, 65.5 mmol) was slowlyadded thereto and the resultant was stirred for 5 hours under roomtemperature under a nitrogen atmosphere. The reaction solution wascooled down to −78° C. and 22.4 g (119 mmol) of 1,2-dibromoethanedissolved in 10 mL anhydrous tetrahydrofuran was slowly added and thenstirred for 5 hours at room temperature.

After the reaction is completed, the solution was concentrated under areduced pressure to remove the solvent and was extracted with distilledwater and dichloromethane, the extract solution was dried with magnesiumsulfite and filtered, and the filtrate was concentrated under a reducedpressure. The reaction solution was recrystallized in n-hexane and then11 g of white solid Intermediate M-3 was obtained as a target compound(yield 75%).

GC-Mass (theoretical value: 245.97 g/mol, measured value: 246 g/mol)

Synthesis of Intermediate M-4

11 g of white solid Intermediate M-4 as a target compound was obtainedusing 10 g (54.3 mmol) of dibenzothiophene instead of the dibenzofuranin the synthesis method of Intermediate M-3 in [Reaction Scheme 4](yield 77%).

GC-Mass (theoretical value: 261.95 g/mol, measured value: 262 g/mol)

Synthesis of Intermediate M-5

27 g of white solid Intermediate M-5 as a target compound was obtainedusing 20 g (94.4 mmol) of 4-dibenzofuranboronic acid instead ofIntermediate M-1 in the synthesis method of Intermediate M-2 in[Reaction Scheme 5] (yield 89%).

LC-Mass (theoretical value: 322.00 g/mol, measured value: M+1=323 g/mol)

Synthesis of Intermediate M-6

25 g of white solid Intermediate M-6 as a target compound was obtainedusing 20 g (87.69 mmol) of 4-dibenzothiopheneboronic acid instead ofIntermediate M-1 in the synthesis method of Intermediate M-2 in[Reaction Scheme 6] (yield 83%).

LC-Mass (theoretical value: 337.98 g/mol, measured value: M+1=338 g/mol)

Synthesis of Intermediate M-7

30 g (178.4 mmol) of a dibenzofuran was added in a round-bottomed flaskand dissolved in 270 g of acetic acid, 29 g (181.5 mmol) of brominedissolved in 6 g of acetic acid was slowly added thereto at 50° C. for 4hours. The reaction solution was further stirred at 50° C. for 8 hoursand cooled down, and then the solution was added in distilled water. Theorange solid was dissolved in dichloromethane and washed with asodiumthiosulfite aqueous solution, the organic layer was driedmagnesium sulfite and filtered, and the filtrate was concentrate underreduced pressure. The product was recrystallized indichloromethane/n-hexane and then 10.1 g of white solid intermediate M-7was obtained as a target compound (yield 23%).

GC-Mass (theoretical value: 245.97 g/mol, measured value: 246 g/mol)

Synthesis of Intermediate M-8

30 g (162.8 mmol) of a dibenzothiophene was added in a round-bottomedflask and dissolved in 2 L of chloroform, then, 27.3 g (170.9 mmol) ofbromine dissolved was slowly added thereto for 6 hours. The reactionsolution was further stirred at 40° C. for 12 hours and cooled down, andthen the solution was added in a sodium thiosulfite aqueous solution.The organic layer was dried with magnesium sulfite and filtered and thefiltrate was concentrated under a reduced pressure. The product wasrecrystallized with ethylacetate/n-hexane and then 15.4 g of white solidIntermediate M-8 was obtained as a target compound (yield 36%).

GC-Mass (theoretical value: 261.95 g/mol, measured value: 262 g/mol)

Synthesis of Intermediate M-9

20 g (127.9 mmol) of 4-chlorophenylboronic acid, 30.0 g (121.5 mmol) ofIntermediate M-7, and 1.48 g (1.28 mmol) of tetrakistriphenylphosphinepalladium were dissolved in 320 ml of toluene and 160 ml of ethanolunder a nitrogen atmosphere, and 160 ml of an aqueous solution including37.7 g (255.8 mmol) of potassium carbonate was added thereto and thenrefluxed and stirred for 12 hours. After the reaction is completed, thereaction solution was extracted with ethylacetate, the extract was driedwith magnesium sulfite and filtered, and then the filtrate wasconcentrated under a reduced pressure. The product was purified withn-hexane/dichloromethane (9:1 volume ratio) through a silica gel columnchromatography and then 28.1 g of white solid Intermediate M-9 wasobtained as a target compound (yield 83%).

LC-Mass (theoretical value: 278.05 g/mol, measured value: M+1=279 g/mol)

Synthesis of Intermediate M-10

30.4 g of white solid Intermediate M-10 as a target compound wasobtained using 32.0 g (121.5 mmol) of Intermediate M-8 instead ofIntermediate M-7 in the synthesis method of Intermediate M-9 in[Reaction Scheme 10] (yield 85%).

LC-Mass (theoretical value: 294.03 g/mol, measured value: M+1=295 g/mol)

Synthesis of Intermediate M-11

30 g (75.3 mmol) of intermediate M-2, 14.0 g (82.83 mmol) of4-aminobiphenyl, 10.9 g (113.0 mmol) of sodium t-butoxide, and 0.46 g(2.26 mmol) of tri-tetra-butylphosphine were dissolved in 750 ml oftoluene, and 0.43 g (0.753 mmol) of Pd(dba)₂ was added, and thenrefluxed and stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 27.5 g of white solidintermediate M-11 was obtained as a target compound (yield 75%).

LC-Mass (theoretical value: 486.21 g/mol, measured value: M+1=487 g/mol)

Synthesis of Intermediate M-12

5.23 g of white solid Intermediate M-12 as a target compound wasobtained using 5 g (17.0 mmol) of Intermediate M-10 instead ofIntermediate M-2 in the synthesis method of Intermediate M-11 in[Reaction Scheme 12] (yield 72%).

LC-Mass (theoretical value: 427.14 g/mol, measured value: M+1=428 g/mol)

Synthesis of Intermediate M-13

4.66 g of white solid Intermediate M-13 as a target compound wasobtained using 1.66 g (17.85 mmol) of aniline instead of 4-aminobiphenylin the synthesis method of Intermediate M-12 in [Reaction Scheme 13](yield 78%).

LC-Mass (theoretical value: 351.11 g/mol, measured value: M+1=352 g/mol)

Synthesis of Intermediate M-14

4.98 g of white solid Intermediate M-14 as a target compound wasobtained using 2.56 g (17.85 mmol) of 1-aminonaphthalene instead of4-aminobiphenyl in the synthesis method of Intermediate M-12 in[Reaction Scheme 14] (yield 73%).

LC-Mass (theoretical value: 401.12 g/mol, measured value: M+1=402 g/mol)

Synthesis of Intermediate M-15

5.05 g of white solid Intermediate M-15 as a target compound wasobtained using 5.49 g (17.0 mmol) of Intermediate M-5 instead ofIntermediate M-10 in the synthesis method of Intermediate M-14 in[Reaction Scheme 15] (yield 77%).

LC-Mass (theoretical value: 385.15 g/mol, measured value: M+1=386 g/mol)

Synthesis of Intermediate M-16

6.0 g of white solid Intermediate M-16 as a target compound was obtainedusing 3.74 g (17.85 mmol) of (9,9-dimethyl-9H-fluoren-2-yl)amine insteadof 1-aminonaphthalene in the synthesis method of Intermediate M-15 in[Reaction Scheme 16] (yield 78%).

LC-Mass (theoretical value: 451.19 g/mol, measured value: M+1=452 g/mol)

Synthesis of Intermediate M-17

25.7 g of white solid Intermediate M-17 as a target compound wasobtained using 11.9 g (82.83 mmol) of 1-aminonaphthalene instead of4-aminobiphenyl in the synthesis method of Intermediate M-11 in[Reaction Scheme 17] (yield 74%).

LC-Mass (theoretical value: 460.19 g/mol, measured value: M+1=461 g/mol)

Synthesis of Intermediate C-10-3

30 g (121.9 mmol) of 3-bromo carbazole, 1.5 equivalents of 2-iodonaphthalene, 0.05 equivalents of a copper catalyst, 0.1 equivalents of1,10-phenanthroline, and 2 equivalents of potassium acetate was put in250 mL of dimethyl formamide in a 500 mL round-bottomed flask and then,heated and refluxed for 18 hours. The reaction solution is cooled down,was added to 1 L of water and then solidified and stirred. The solid wasfiltered and recrystallized with 500 mL of ethyl acetate to obtain 34 gof Intermediate C-10-3.

LC/MS calculated for: C22H14BrN Exact Mass: 371.0310, found for: 372.05[M+H].

Synthesis of Intermediate C-10-2

34 g (91.33 mmol) of the synthesized Intermediate C-10-3 was dissolved200 mL of anhydrous tetrahydrofuran in a 500 mL round-bottomed flask,and a temperature was down to −78° C. under a nitrogen atmosphere. 1.3equivalents of a butyl lithium solution was added in a dropwise fashionand was stirred for 30 minutes, 1.5 equivalents of triisopropylboratewas added in a dropwise fashion and was stirred for 1 hour, and atemperature is up to room temperature and the resultant was stirred for2 hours. 100 mL of water was slowly added to the reaction solution andlayer separated to separate an organic layer. The aqueous layer wasextracted with 100 mL of ethyl acetate, and the organic layer wascollected, washed with 100 mL of salt-saturated water, was dried withanhydrous magnesium sulfate, and then filtered and concentrated.

The concentrated residue was vacuum-dried to obtain 33 g of IntermediateC-10-2 which was used without additional purification in the nextreaction.

Synthesis of Intermediate C-10-1

33 g of the synthesized Intermediate C-10-2 was put in a 500 mLround-bottomed flask, 1.5 equivalents of 4-bromo-iodo benzene, 0.05equivalents of tetrakistriphenyl phosphine palladium, 2.5 equivalents ofpotassium carbonate were suspended in a mixed solution of 200 mL oftetrahydrofuran and 70 mL of water and heated and refluxed under anitrogen atmosphere. The reaction solution was cooled down, the aqueouslayer was removed, and then the organic layer was collected andconcentrated. The concentrated residue was purified with a mixedsolution of normal hexane and ethyl acetate with a silica gel column toobtain 37 g of Intermediate C-10-1.

LC/MS calculated for: C28H18BrN, Exact Mass: 447.0623, found for:447.10.

Synthesis Example 10: Synthesis of Compound A-414

5 g (20.2 mmol) of Intermediate M-3, 9.85 g (20.2 mmol) of IntermediateM-11, 2.91 g (30.3 mmol) of sodium t-butoxide, and 0.12 g (2.26 mmol) oftri-tetra-butylphosphine were dissolved in 200 ml of toluene, 0.12 g(0.202 mmol) of Pd(dba)₂ was added, and then refluxed and stirred for 12hours under a nitrogen atmosphere.

After the reaction, the reactant was extracted with ethylacetate anddistilled water, an organic layer was dried with magnesium sulfite andfiltered, and the filtrate was concentrate under a reduced pressure. Theproduct was purified with n-hexane/dichloromethane (7:3 volume ratio)through a silica gel column chromatography and then 12 g of white solidA-414 was obtained as a target compound (yield 91%).

LC-Mass (theoretical value: 652.25 g/mol, measured value: M+1=653 g/mol)

Synthesis Example 11: Synthesis of Compound A-415

11.8 g of white solid A-415 as a target compound was obtained using 5.3g (20.2 mmol) of Intermediate M-4 instead of Intermediate M-3 inSynthesis Example 10 (yield 87%).

LC-Mass (theoretical value: 668.23 g/mol, measured value: M+1=669 g/mol)

Synthesis Example 12: Synthesis of Compound A-9

11.8 g of white solid A-9 as a target compound was obtained using 5.3 g(20.2 mmol) of Intermediate M-8 instead of Intermediate M-3 in SynthesisExample 10 (yield 87%).

LC-Mass (theoretical value: 668.23 g/mol, measured value: M+1=669 g/mol)

Synthesis Example 13: Synthesis of Compound A-10

12.4 g of white solid A-10 as a target compound was obtained using 6.5 g(20.2 mmol) of Intermediate M-5 instead of Intermediate M-3 in SynthesisExample 10 (yield 84%).

LC-Mass (theoretical value: 728.28 g/mol, measured value: M+1=729 g/mol)

Synthesis Example 14: Synthesis of Compound A-11

13.2 g of white solid A-11 as a target compound was obtained using 6.85g (20.2 mmol) of Intermediate M-6 instead of Intermediate M-3 inSynthesis Example 10 (yield 88%).

LC-Mass (theoretical value: 744.26 g/mol, measured value: M+1=745 g/mol)

Synthesis Example 15: Synthesis of Compound A-18

6.53 g (20.2 mmol) of Intermediate M-5 and 9.30 g (20.2 mmol) ofIntermediate M-17, 2.91 g (30.3 mmol) of sodium t-butoxide, and 0.12 g(2.26 mmol) of tri-tetra-butylphosphine were dissolved in 200 ml oftoluene, 0.12 g (0.202 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethyl acetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 12.5 g of white solid A-18 wasobtained as a target compound (yield 88%).

LC-Mass (theoretical value: 702.27 g/mol, measured value: M+1=703 g/mol)

Synthesis Example 16: Synthesis of Compound A-19

12.3 g of white solid A-19 as a target compound was obtained using 6.85g (20.2 mmol) of Intermediate M-6 instead of Intermediate M-5 inSynthesis Example 15 (yield 85%).

LC-Mass (theoretical value: 718.24 g/mol, measured value: M+1=719 g/mol)

Synthesis Example 17: Synthesis of Compound A-327

5.2 g (12.2 mmol) of Intermediate M-12 and 3.0 g (12.2 mmol) ofIntermediate M-7, 1.76 g (18.3 mmol) of sodium t-butoxide, and 0.074 g(0.37 mmol) of tri-tetra-butylphosphine were dissolved in 120 ml oftoluene, 0.070 g (0.122 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 6.2 g of white solid A-327 wasobtained as a target compound (yield 86%).

LC-Mass (theoretical value: 593.18 g/mol, measured value: M+1=594 g/mol)

Synthesis Example 18: Synthesis of Compound A-335

4.3 g (12.2 mmol) of Intermediate M-13 and 4.14 g (12.2 mmol) ofIntermediate M-6, 1.76 g (18.3 mmol) of sodium t-butoxide, and 0.074 g(0.37 mmol) of tri-tetra-butylphosphine were dissolved in 120 ml oftoluene, 0.070 g (0.122 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 6.8 g of white solid A-335 wasobtained as a target compound (yield 91%).

LC-Mass (theoretical value: 609.16 g/mol, measured value: M+1=610 g/mol)

Synthesis Example 19: Synthesis of Compound A-340

4.9 g (12.2 mmol) of Intermediate M-14 and 3.94 g (12.2 mmol) ofIntermediate M-5, 1.76 g (18.3 mmol) of sodium t-butoxide, and 0.074 g(0.37 mmol) of tri-tetra-butylphosphine were dissolved in 120 ml oftoluene, 0.070 g (0.122 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 7.2 g of white solid A-340 wasobtained as a target compound (yield 92%).

LC-Mass (theoretical value: 643.20 g/mol, measured value: M+1=644 g/mol)

Synthesis Example 20: Synthesis of Compound A-373

5.51 g (12.2 mmol) of Intermediate M-16 and 3.21 g (12.2 mmol) ofIntermediate M-8, 1.76 g (18.3 mmol) of sodium t-butoxide, and 0.074 g(0.37 mmol) of tri-tetra-butylphosphine were dissolved in 120 ml oftoluene, 0.070 g (0.122 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 7.0 g of white solid A-373 wasobtained as a target compound (yield 91%).

LC-Mass (theoretical value: 633.21 g/mol, measured value: M+1=634 g/mol)

Synthesis Example 21: Synthesis of Compound A-376

4.7 g (12.2 mmol) of Intermediate M-15 and 3.01 g (12.2 mmol) ofIntermediate M-3, 1.76 g (18.3 mmol) of sodium t-butoxide, and 0.074 g(0.37 mmol) of tri-tetra-butylphosphine were dissolved in 120 ml oftoluene, 0.070 g (0.122 mmol) of Pd(dba)₂ was added, and then refluxedand stirred for 12 hours under a nitrogen atmosphere. After thereaction, the reactant was extracted with ethylacetate and distilledwater, an organic layer was dried with magnesium sulfite and filtered,and the filtrate was concentrate under a reduced pressure. The productwas purified with n-hexane/dichloromethane (7:3 volume ratio) through asilica gel column chromatography and then 6.2 g of white solid A-376 wasobtained as a target compound (yield 92%).

LC-Mass (theoretical value: 551.19 g/mol, measured value: M+1=552 g/mol)

Synthesis Example 22: Synthesis of Compound C10

37 g (82.52 mmol) of Intermediate C-10-1, 1.2 equivalents of dibiphenylamine, 0.05 equivalents of dibenzylidine acetone bispalladium, and 1.5equivalents of sodium tertiary butoxide were put in a 500 mLround-bottomed flask, 250 mL of xylene was added, and then refluxed andstirred for 18 hours under a nitrogen atmosphere. The reaction solutionis cooled down, was diluted in 1 L of methanol, and then was stirred.The produced solids were filtered. The solides were washed with 300 mLof water and 300 mL of methanol, solids are collected, andrecrystallized with 50 mL of methylene chloride and 300 mL of hexane toobtain 43 g of Compound C10.

LC/MS calculated for: C₅₂H₃₆N₂ Exact Mass: 688.2878, found for: 688.29.

Synthesis Example 23: Synthesis of Compound C31

10 g (30.9 mmol) of Intermediate M-5 and 9.9 g (30.9 mmol) ofbis(4-biphenyl)amine, and 4.5 g (46.35 mmol) of sodium t-butoxide wereput in a round-bottomed flask and 155 ml of toluene was added, and theywere dissolved therein. 0.178 g (0.31 mmol) of Pd(dba)₂ and 0.125 g(0.62 mmol) of tri-tertiary-butylphosphine were sequentially addedthereto, and then refluxed and stirred for 4 hours under a nitrogenatmosphere. After the reaction is completed, it was extracted withtoluene and distilled water, the organic layer was dried with magnesiumsulfate and filtered, and the filterate was concentrated under reducedpressure. The product was purified with n-hexane/dichloromethane (8:2volume ratio) through a silica gel column chromatography and then 16 gof Compound C31 was obtained as a target compound (yield 92%).

LC-Mass (theoretical value: 563.22 g/mol, measured value: M+=563.28g/mol)

Manufacture of Organic Light Emitting Diode I—Green Diode Example 1

A glass substrate coated with ITO (indium tin oxide) as a 1500 Å-thickthin film was ultrasonic wave-washed with distilled water. After washingwith the distilled water, the glass substrate was ultrasonic wave-washedwith a solvent such as isopropyl alcohol, acetone, methanol, and thelike and dried and then, moved to a plasma cleaner, cleaned by usingoxygen plasma for 10 minutes, and moved to a vacuum depositor. Thisobtained ITO transparent electrode was used as an anode, a 700 ÅA-thickhole injection layer was formed on the ITO substrate by vacuumdepositing Compound A, and a hole transport layer was formed on theinjection layer by depositing Compound B to be 50 Å thick and Compound Cto be 1020 Å thick. On the hole transport layer (HTL), a 400 Å-thicklight emitting layer was formed by vacuum-depositing Compound 1 ofSynthesis Example 1 and Compound A-414 of Synthesis Example 10simultaneously as a host and 10 wt % oftris(2-phenylpyridine)iridium(III) [Ir(ppy)₃] as a dopant. Herein,Compound 1 and Compound A-414 were used in a weight ratio of 3:7, buttheir ratio in the following Examples was separately provided.Subsequently, on the light emitting layer, a 300 Å-thick electrontransport layer was formed by simultaneously vacuum-depositing thecompound D and Liq in a ratio of 1:1, and on the electron transportlayer, Liq and Al were sequentially vacuum-deposited to be 15 Å thickand 1200 Å thick, manufacturing an organic light emitting diode.

The organic light emitting diode had a structure of 5-layered organicthin films specifically as follows.

ITO/Compound A (700 Å)/Compound B (50 Å)/Compound C (1020Å)/EML[Compound 1:A-414:Ir(ppy)₃=27 wt %:63 wt %:10 wt %] (400Å)/Compound D:Liq (300 Å)/Liq (15 Å)/Al (1200 Å).

-   Compound A:    N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4′-diamine-   Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile    (HAT-CN),-   Compound C:    N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine-   Compound D:    8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

Example 2 to Example 16

Each organic light emitting diode according to Example 2 to Example 6were manufactured according to the same method as Example 1 by using thefirst hosts and the second hosts as shown in Table 1 in eachcorresponding ratio.

Comparative Example 1 to Comparative Example 10

Each organic light emitting diode according to Comparative Examples 1 to10 was manufactured according to the same method as Example 1 by usingthe first hosts as single hosts as shown in Table 1.

Comparative Example 11

An organic light emitting diode was manufactured according to the samemethod as Example 1 by using Compound A-414 and Comparative ExampleCompound I in a ratio of 5:5 as a host.

Comparative Example Compound I

Comparative Example 12

An organic light emitting diode was manufactured according to the samemethod as Example 1 by using Compound 1 and mCP(1,3-bis(N-carbazolyl)benzene) in a ratio of 5:5 as a host.

Manufacture of Organic Light Emitting Diode II-Red Diode Example 17

An organic organic light emitting diode according to Example 17 wasmanufactured according to the same method as Example 1, except for usinga mixture of Compound 181 of Synthesis Example Ad-1 and Compound C31 ofSynthesis Example 23 in a weight ratio of 3:7 as a host and doping adopant, 5 wt % of [Ir(piq)₂acac] to form a light emitting layer.

Example 18 to Example 20

Each organic light emitting diode according to Example 18 to Example 20were manufactured according to the same method as Example 17 by usingthe first hosts and the second hosts as shown in Table 2 in eachcorresponding ratio.

Comparative Example 13 to Comparative Example 15

Each organic light emitting diode according to Comparative Examples 13to 15 was manufactured according to the same method as Example 17 byusing the first hosts as single hosts as shown in Table 2.

Evaluation 1: Luminous Efficiency and Life-span Increase Effect

Luminous efficiency and life-span characteristics of the organic lightemitting diodes according to Examples 1 to 20 and Comparative Examples 1to 15 were evaluated. Specific measurement methods are as follows, andthe results are shown in Tables 1 and 2.

(1) Measurement of Current Density Change Depending on Voltage Change

The obtained organic light emitting diodes were measured regarding acurrent value flowing in the unit device, while increasing the voltagefrom 0 V to 10 V using a current-voltage meter (Keithley 2400), and themeasured current value was divided by area to provide the results.

(2) Measurement of Luminance Change Depending on Voltage Change

Luminance was measured by using a luminance meter (Minolta Cs-1000A),while the voltage of the organic light emitting diodes was increasedfrom 0 V to 10 V.

(3) Measurement of Luminous Efficiency

Current efficiency (cd/A) at the same current density (10 mA/cm²) werecalculated by using the luminance, current density, and voltages (V)from the items (1) and (2).

(4) Measurement of Life-Span

T90 life-spans of the organic light emitting diodes according toExamples 1 to 20 and Comparative Examples 1 to 15 were measured as atime when their luminance decreased down to 90% relative to the initialluminance (cd/m²) after emitting light with 5000 cd/m² as the initialluminance (cd/m²) and measuring their luminance decrease depending on atime with a Polanonix life-span measurement system.

(5) Measurement of Driving Voltage

Driving voltage of each organic light emitting diode was measured at 15mA/cm² by using a current-voltage meter (Keithley 2400), and the resultsare provided in Tables 1 and 2.

TABLE 1 Green Diode Data Ratio of First host + Life- Driving SecondSecond Efficiency span voltage First host host host Color (Cd/A) T90(Vd) Example 1 1 A-414 3:7 green 54 235 3.9 Example 2 2 A-414 3:7 green49 244 4.1 Example 3 2 C31 3:7 green 61 250 3.6 Example 4 3 A-415 3:7green 52 261 4.3 Example 5 100 A-9 3:7 green 51 280 4.2 Example 6 4 A-102:8 green 48 291 3.9 Example 7 4 C31 2:8 green 49 311 3.7 Example 8 16A-11 2:8 green 53 231 3.8 Example 9 16 C31 2:8 green 62 352 3.6 Example16 C10 2:8 green 55 309 3.7 10 Example 126 A-18 2:8 green 49 278 4.2 11Example 126 C31 2:8 green 55 334 3.7 12 Example 140 A-19 3:7 green 48257 4.3 13 Example 140 C10 3:7 green 51 319 3.7 14 Example 113 A-327 3:7green 47 281 4.1 15 Example 113 C31 3:7 green 61 376 3.8 16 Comparative1 — — green 35 71 4.8 Example 1 Comparative 2 — — green 35 80 4.9Example 2 Comparative 4 — — green 37 75 5.1 Example 3 Comparative 16 — —green 40 77 4.7 Example 4 Comparative 126 — — green 33.6 10 4.5 Example5 Comparative 113 — — green 20.6 32 4.7 Example 6 Comparative A-414 — —green 18 15 6.2 Example 7 Comparative A-415 — — green 19 18 6.4 Example8 Comparative C31 — — green 21 19 5.9 Example 9 Comparative C10 — —green 22 23 6.8 Example 10 Comparative Comparative A-414 5:5 green 38 545.1 Example Example 11 compound I Comparative 1 mCP 5:5 green 40 75 4.8Example 12

TABLE 2 Red Diode Data Ratio of First host + Life- Driving SecondEfficiency span voltage First host Second host host Color (Cd/A) T90(Vd) Example 181 C31 3:7 red 23 450 3.6 17 Example 180 A-414 3:7 red 21400 3.6 18 Example 183 C31 3:7 red 22 380 3.94 19 Example 190 C31 3:7red 20 350 3.9 20 Comparative 181 — 100 red 12 25 6.6 Example 13Comparative C31 — 100 red 11 33 7.9 Example 14 Comparative A-414 — 100red 9 30 8.1 Example 15

Referring to Tables 1 and 2, the host combination of the presentinvention showed remarkably improved luminous efficiency, life-span, anddriving voltage compared with a single host.

While this invention has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims. Therefore, the aforementioned embodimentsshould be understood to be exemplary but not limiting the presentinvention in any way.

1. A composition for an organic optoelectronic device, comprising atleast one first compound represented by formula 1; and at least onesecond compound represented by formula 2:

wherein, in formula 1, X¹¹ to X¹² are independently N, C, or CR^(a), atleast one of X¹ to X⁶ is N, at least one of X⁷ to X¹² is N, R^(a)'s areindependently hydrogen, deuterium, a substituted or unsubstituted C1 toC30 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group,a substituted or unsubstituted C1 to C30 alkynyl group, a substituted orunsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 toC30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthiogroup, a substituted or unsubstituted C2 to C30 heteroaryl group, ahydroxyl group, a thiol group, or a combination thereof, R^(a)'s areindependently present or adjacent R^(a)'s are linked with each other toprovide a ring, and L¹ is a C6 to C30 arylene group that isunsubstituted or substituted with deuterium, a C1 to C40 silyl group, aC1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30heterocycloalkyl group, or a C6 to C30 aryl group;

wherein, in formula 2, L² to L⁴ are independently a single bond, asubstituted or unsubstituted C6 to C30 arylene group, or a substitutedor unsubstituted C2 to C30 heteroarylene group, Ar¹ to Ar³ areindependently, a substituted or unsubstituted C6 to C30 aryl group, asubstituted or unsubstituted C2 to C30 heterocyclic group, or acombination thereof, and when specific definition is not otherwiseprovided, “substituted” of formulas 1 and 2 refers to replacement of atleast one hydrogen by deuterium, a halogen, a hydroxyl group, an aminogroup, a C1 to C30 amine group, a C6 to C30 arylamine group, a nitrogroup, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 to C30cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30 arylgroup, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a C1 toC10 trifluoroalkyl group, or a cyano group.
 2. The composition for anorganic optoelectronic device of claim 1, wherein formula 1 isrepresented by one of formula 1-I to formula 1-IV:

wherein, in formulas 1-I to 1-IV, Z's are independently N, or CR^(a), ineach ring including Z, at least one Z is N, R^(a), R^(a1) to R^(a4),R^(c), R^(d), R^(e), R^(f), R^(g), and R^(h) are independently hydrogen,deuterium, a substituted or unsubstituted C1 to C30 alkyl group, asubstituted or unsubstituted C6 to C30 aryl group, a substituted orunsubstituted C2 to C30 heteroaryl group, or a combination thereof, L¹is a C6 to C30 arylene group that is unsubstituted or substituted withdeuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C3 to C30cycloalkyl group, a C2 to C30 heterocycloalkyl group, or a C6 to C30aryl group, and when specific definition is not otherwise provided,“substituted” is the same as defined in claim
 1. 3. The composition foran organic optoelectronic device of claim 1, wherein L¹ is a phenylenegroup that is unsubstituted or substituted with deuterium, a C1 to C40silyl group, a C1 to C30 alkyl group, or a C6 to C30 aryl group; abiphenylene group that is unsubstituted or substituted with deuterium, aC1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 to C30 arylgroup; a terphenylene group that is unsubstituted or substituted withdeuterium, a C1 to C40 silyl group, a C1 to C30 alkyl group, or a C6 toC30 aryl group; or a quaterphenylene group that is unsubstituted orsubstituted with deuterium, a C1 to C40 silyl group, a C1 to C30 alkylgroup, or a C6 to C30 aryl group.
 4. The composition for an organicoptoelectronic device of claim 1, wherein L¹ is a substituted orunsubstituted linker selected from groups of Group 2: [Group 2]

wherein, in Group 2, * is a linking point with an adjacent atom.
 5. Thecomposition for an organic optoelectronic device of claim 1, wherein X¹to X¹² of formula 1 are independently N, C, or CR^(a), three of X¹ to X⁶are N, three of X⁷ to X¹² are N, R^(a)'s are independently hydrogen,deuterium, a substituted or unsubstituted C1 to C30 alkyl group, asubstituted or unsubstituted C6 to C30 aryl group, a substituted orunsubstituted C2 to C30 heteroaryl group, or a combination thereof, andL¹ is a C6 to C30 arylene group that is unsubstituted or substitutedwith deuterium, a C1 to C30 alkyl group, or a C6 to C30 aryl group,wherein when specific definition is not otherwise provided,“substituted” refers to replacement of at least one hydrogen bydeuterium, a halogen, a hydroxyl group, a C1 to C40 silyl group, a C1 toC30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30heterocycloalkyl group, a C6 to C30 aryl group, or a C2 to C30heterocyclic group.
 6. The composition for an organic optoelectronicdevice of claim 5, wherein R^(a)'s are a substituted or unsubstituted C6to C30 aryl group, and the C6 to C30 aryl group is a substituted orunsubstituted phenyl group, a substituted or unsubstituted biphenylgroup, a substituted or unsubstituted terphenyl group, a substituted orunsubstituted quaterphenyl group, a substituted or unsubstitutednaphthyl group, a substituted or unsubstituted anthracenyl group, asubstituted or unsubstituted fluorenyl group, a substituted orunsubstituted triphenylene group, or a substituted or unsubstitutedphenanthrenyl group.
 7. The composition for an organic optoelectronicdevice of claim 1, wherein L² to L⁴ of formula 2 are independently asingle bond, a substituted or unsubstituted phenylene group, asubstituted or unsubstituted biphenylene group, a substituted orunsubstituted naphthyl group, a substituted or unsubstituted fluorenylgroup, a substituted or unsubstituted pyridinyl group, a substituted orunsubstituted pyrimidinyl group, a substituted or unsubstitutedquinolinyl group, or a combination thereof, Ar¹ to Ar³ are independentlya substituted or unsubstituted phenyl group, a substituted orunsubstituted biphenyl group, a substituted or unsubstituted terphenylgroup, a substituted or unsubstituted quaterphenyl group, a substitutedor unsubstituted naphthyl group, a substituted or unsubstitutedfluorenyl group, a substituted or unsubstituted carbazolyl group, asubstituted or unsubstituted dibenzofuranyl group, a substituted orunsubstituted dibenzothiophenyl group, a substituted or unsubstitutedanthracenyl group, a substituted or unsubstituted phenanthrenyl group, asubstituted or unsubstituted triphenylene group, a substituted orunsubstituted quinolinyl group, a substituted or unsubstituted pyridinylgroup, a substituted or unsubstituted pyrimidinyl group, a substitutedor unsubstituted thiophenyl group, or a combination thereof.
 8. Thecomposition for an organic optoelectronic device of claim 7, wherein Ar¹to Ar³ of formula 2 are selected from substituted or unsubstitutedgroups of Group 4: [Group 4]

wherein, in Group 4, * is a linking point with an adjacent atom.
 9. Thecomposition for an organic optoelectronic device of claim 1, wherein thefirst compound is represented by formulas 1-I a to 1-IVa, and the secondcompound is formula 2 wherein L² to L⁴ are independently a single bond,or a substituted or unsubstituted phenylene group, and Ar¹ to Ar³ areindependently a substituted or unsubstituted C6 to C30 aryl group, or asubstituted or unsubstituted C2 to C30 heterocyclic group, provided thatat least one of Ar¹ to Ar³ is a substituted or unsubstituted C2 to C30heterocyclic group:

wherein, in formulas 1-Ia and 1-IVa, Z¹ to Z⁶ are independently N, orCR^(a), at least two of Z¹ to Z³ are N, at least two of Z⁴ to Z⁶ are N,R^(a)'s and R^(a1) to R^(a4) are independently hydrogen, or asubstituted or unsubstituted C6 to C30 aryl group, L is a C6 to C30arylene group that is substituted or unsubstituted with deuterium, a C1to C30 alkyl group, or a C6 to C30 aryl group, and when specificdefinition is not otherwise provided, “substituted” is the same asdefined in claim
 1. 10. The composition for an organic optoelectronicdevice of claim 1, wherein the composition further includes aphosphorescent dopant.
 11. An organic optoelectronic device, comprisingan anode and a cathode facing each other, and at least one organic layerdisposed between the anode and the cathode, wherein the organic layerincludes the composition for an organic optoelectronic device ofclaim
 1. 12. The organic optoelectronic device of claim 11, wherein theorganic layer includes a light emitting layer, the light emitting layerincludes the composition for an organic optoelectronic device.
 13. Adisplay device comprising the organic optoelectronic device of claim 11.